DE2908627A1 - NEW TRISHYDROXYALKYLHETEROCYCLES - Google Patents

Abstract

New tris-hydroxyalkyl triazolidine-3,5-diones are obtained by reacting triazolidine-3,5-dioxy with alkylene oxides.

Description

BAYER AKTIENGESELLSCHAFT Central area Patents, trademarks and licenses

5090 Leverkusen, Bayerwerk

Str-by

3, ^r JSa 1379

New trishydroxyalky! Heterocyclic compounds

The present invention relates to new N-heterocyclic ones Triols of the general formula

R ³ R ¹

it HO — C — CjN

η 2

C N

R ¹ R ³ C - C -

- H

U)

- R "

N - C - C - Ot - H

Lr R ⁴ -1

n.

wherein

5 n _Q , n ^ and n _2, identical or different for an integer

from 1 to 30, - preferably 1-10,

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I ₁ .

3 4

R, R, R and R, identical or different, independently of one another, represent hydrogen, an aliphatic C ₁ -C ₁₀ , cycloaliphatic ^C 4 ~ ^C 8 ^or araliphatic C ₇ -C ₁₇ radical which is optionally substituted by halogen

_{or an aromatic C, -C, c} radical which is optionally substituted by halogen, alkyl and / or alkoxy. Preferably

1 ⁶ 2 ¹⁶ T 4
mean R, R, R and R hydrogen, one optionally with halogen (chlorine,

Bromine) -substituted alkyl radical with C _{1 -C., Preferably methyl, ethyl or a Cg-C 1} optionally substituted with halogen atoms (chlorine, bromine) Cj-C ^ -alkyl radicals and / or with C ..- C * alkoxy groups,

Aryl radical, preferably phenyl.

The residues of ethylene and propylene oxide units with a degree of oxyalkylation are particularly preferably derived η = 1 from.

The triols of the general formula I according to the invention are new and are obtained by adding triazolidinedione-3,5 (= üracol) with alkylene oxides, preferably ethylene oxide, Propylene oxide, butylene oxide, styrene oxide, if appropriate in the presence of a suitable catalyst. It can however, the thione analogs of uracol can also be used. The addition of the alkylene oxide to the three NH

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Groups of the triazolidinedione-3,5 can be used both in the presence acidic as well as alkaline catalysts. However, preference is given to using the Preparation of the triols of the formula I, basic catalysts such as tetraethylammonium chloride, tertiary amines such as triethylamine and dimethylaniline and alkali or alkaline earth metal hydroxides or their carbonates such as calcium hydroxide or Potassium carbonate. However, alkali halides such as lithium chloride can also be used. The amount of catalyst is between 0.05 and 3% based on the reactants.

A preferred embodiment is the addition of three moles of ethylene oxide to one mole of uracol without the use of a catalyst, practically quantitative formation of N _f N ', N "-Tris-hydroxyethyluracol taking place. This reaction is all the more surprising since the three NH the uracol should have a different reactivity due to their different basicity, according to which an addition of the ethylene oxide to already existing hydroxyl groups and thus the formation of polyether structural units would be expected. The addition of the ethylene oxide to the uracol can be followed very well in the absence of a catalyst , since after 3 moles of ethylene oxide have been consumed under normal pressure hardly any more ethylene oxide is absorbed.The preparation of the trishydroxy compounds according to formula I is preferably carried out using equivalent amounts, ie 3 Cn ^ n ₁ + n ₂ ) moles of alkylene oxide are used per mole of uracol.

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The 3,5-triazolidinedione used to prepare the new triols of the formula I is known from the literature and can be obtained from hydrazine-N, N'-dicarboxylic acid ^{diamide with elimination of ammonia, for example by heating to above 20O 0 C.}

The reaction of the uracol with the alkylene oxide is preferably carried out in inert organic solvents. Polar organic solvents such as dimethyl sulfoxide, tetramethylene sulfone, Dimethylformamide / dimethylacetamide and N-methylpyrrolidione-2. Another very suitable solvent is water, surprisingly no reaction of the Ethylene oxide is observed with the water. It is not absolutely necessary to dissolve the üracol 5 to bring with the alkylene oxide in reaction. The reaction can also take place with a uracol suspension, whereby the triol formed then goes into solution, so that the end of the reaction is indicated by a clear solution will. Uracol and alkylene oxide can also be added together to the resulting triol solution, so that the The amount of solvent is kept very low. The amount of solvent should be used for economic reasons be very low and can be between 0.3 parts by weight and 20 parts by weight of solvent, based on one part by weight of reactants. After the reaction is complete, this will be Solvent removed by applying a vacuum and the remaining, viscous residue purified by customary working methods such as recrystallization. Often can

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However, cleaning can be dispensed with and the raw product is processed further immediately.

The reaction is preferably carried out at temperatures from 25 ° C to 2OO ° C, particularly preferably at 8O ⁰ C to 15O ° C.

The reaction times are generally between 30 Minutes and several days, but in special cases they can also be higher or lower. Through appropriate Choice of reaction conditions, e.g. pressure, shorter reaction times are achieved.

A particularly preferred embodiment is the reaction of uracol in a lower dialkylformamide (for example dimethylformamide) with ethylene oxide at a temperature of 120.degree. The solvent is removed after the reaction in a water jet vacuum and then concentrated at 0.2 mbar and 90-100 ⁰ C to constant weight. The resulting viscous residue crystallizes very quickly and can be filtered off with suction after being suspended in ethanol or isopropanol. The almost pure tris-2-hydroxyethyl-triazolidinedione-3,5 obtained can be further purified by recrystallization in acetone or isopropanol.

The tris-2-hydroxyalkyl-triazolidinediones of the formula I. are valuable starting products for the production of

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polymeric compounds. They can be used as crosslinkers in known hydroxyl-containing polyesters from e.g. Adipic acid, phthalic acid, diglycol are incorporated and are used in the production of rigid or flexible foam polyurethanes used.

The compounds of the formula I according to the invention, in particular when η = 1, can be used as starters for the preparation of hydroxyl-containing polyethers and, in turn, depending on the molecular weight, for the production of Rigid or flexible foam polyurethanes can be used.

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example 1

In a 500 ml three-necked flask equipped with a stirrer, thermometer and a water-cooled reflux condenser, 50.5 g (0.5 mol) of uracol are dissolved in 150 ml of dimethylformamide. 66 g (1.5 mol) of ethylene oxide are passed into this solution at 120 ° C. in such a way that no ethylene oxide escapes through a bubble counter placed on the reflux condenser. After the reaction has ended, the mixture is concentrated to constant weight in vacuo, finally at 0.2 mbar / 100 ° C. This gives 117 g of a viscous liquid which, according to gas chromatography, contains over 85% of the pure tris-hydroxyethyl-triazolidine-3,5-dione, which gradually crystallizes out after the viscous residue is left to stand. The pure tris-hydroxyethyl-3,5-triazolidindion mp = 90 ⁰ C is also obtained by the viscous crude product dissolved in isopropanol and druch cooling, it is brought to crystallization. IR and NMR spectra as well as the elemental analysis agree with the assumed structure.

Calc .: 41.2% C 6.4% H 18% N 21.9% OH Found: 41.4 = C 6.5% H 17.9% N 21.7% OH

Example 2

In a pressure vessel, a mixture of 303 g {3 mol) uracol, 30 g powdered caustic soda and 45Ο ml

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Dimethylformamide at 105 ^° C. 1000 g of propylene oxide are metered in such that the internal pressure does not rise above 8 bar. After the reaction has ended, the volatile constituents are removed in vacuo, finally at 0.2 mbar and 100 ^{° C.}

The residue is dissolved in chloroform, _{neutralized with dilute H 2} SO ₄ , the precipitated sodium sulfate is filtered off and the solvent is removed in vacuo to constant weight. 1272 g (= 97.7% yield) of a yellowish, oily polyether with a viscosity V \ i 25 = 8692 mPa.s are obtained, the IR spectrum of which agrees with the assumed structure. The analysis showed a hydroxyl content of 12% (calculated: 12.1%) and a nitrogen content of 9.8% (calculated 9.9%).

Example 3

50.5 g (0.5 mol) of uracol are placed in a three-necked flask, which is equipped with a stirrer, thermometer and reflux condenser, dissolved in 150 ml of dimethylformamide and with 2.5 g of tetraethylammonium chloride are added. 108 g of isobutylene oxide are added dropwise to this mixture at 120.degree and stirred at 120 ° C. for 2 hours. After this Removal of the volatile constituents in vacuo, finally at O, 2 mbar and 100 ° C, 158 g of a light yellow, obtained viscous residue, the IR spectrum of which agrees with the assumed structure. The analysis

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resulted in a hydroxyl content of 15.9% OH (calculated 16.1% OH), while the elemental analysis showed the following values:

calculated! 53.0% C, 8.52% H, 13.25% N found: 52.8% C, 8.44% H, 13.5% N

Example 4

50.5 g (0.5 mol} uracol are placed in a three-necked flask, which is equipped with a stirrer, thermometer and reflux condenser, dissolved in 150 g of water. After adding 0.5 g of endoethylene piperazine are refluxed Solvent 66 g (1.5 mol) of ethylene oxide passed in such a way that no ethylene oxide escapes. After the The reaction is carried out in vacuo, finally at 0.2 mbar / 80 ° C restricted to constant weight. 115 g of a viscous liquid are obtained in this way, the It. Gas chromatogram approx. 75% of the pure tris-hydroxyethyl-triazolidinedione-3,5 contains.

Example 5

Analogously to Example 4, 50.5 g of uracol are dissolved in 150 g of dimethylformamide dissolved, treated with 0.75 g of lithium chloride and reacted with 66 g of ethylene oxide. After being constricted 114 g of a viscous liquid that begins to criticize after a few hours and which it. Gas chromatogram 82% of pure tris-hydroxyethyltriazolidinedione-3,5 contains.

Example 6

In a three-necked flask which is cooled with a stirrer, thermometer and a dry ice / methanol mixture A reflux condenser is provided, 1010 g (10 mol) of uracol are suspended in 1000 g of dimethylformamide and mixed with 30 g of triethylamine are added.

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At 12O ° e a total of 1320 g of ethylene oxide are then so initiated that there is a slight reflux and that the meanwhile strongly exothermic The reaction can be kept at 120 ° C. by cooling with air. After the reaction has ended, in vacuo finally concentrated to constant weight at 0.2 mbar and 80 ° C. There were 2330 g of a viscous The solution obtained which crystallized through the next day and which, according to gas chromatographic analysis, was 85% contains pure tris-2-hydroxyethyl-triazolidinedione-3,5.

Example 7

505 g of uracol were suspended in a three-necked flask (test arrangement analogous to Example 6) in 1500 g of tetramethylene sulfone, and 10 g of tetraethylammonium chloride were added. A clear solution was formed by introducing ethylene oxide at 120.degree. Then another 303 g uracol were suspended and as soon as a clear solution had formed again, another 202 g uracol were added. After a total of 1310 g of ethylene oxide were introduced, was evaporated in vacuo, finally at 0.2 mbar and 120 ⁰ C and concentrated. This gave 2,354 g of a viscous liquid which, according to gas chromatographic analysis, contained 84.5% of pure tris-2-hydroxyethyl-triazolidinedione-3,5.

By dissolving the viscous liquid in a mixture of isopropanol and acetone and the following Cooling down, a crystalline substance with a melting point of 86-88 ° C can be obtained, which can be obtained by recrystallization from e.g. isopropanol a melting point of

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Reached 9O ° C and the It IR spectrum with the pure Tris-2-hydroxyethyl-triazolidinedione-3,5 from Example 1 corresponds.

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Claims (3)

Claims 1. Trishydroxyalkylheterocycles of the general formula I H — f-0— η
2 R ³ R ¹ ti c— οι. U ■ Ν N-- R ¹ R ³ I I C - C - »2 U -Tj R ¹ R ³ c - LoL (D wherein n _Q , η- and n ~, identical or different _t for a number from 1 to 30, 12 3 4
R, R, R and R the same or different for hate substance, an optionally substituted with halogen, aliphatic ^ cycloali— phatic or araliphatic radical or one optionally substituted by halogen, alkyl and / or alkoxy aromatic residue. Le A 19 1Ο1 030037/0281 -V- 2. Tris-hydroxyalkyl-triazolidine-S / S-diones of the general Formula I, in the η, η., and n ₂ each represent 1. 3. Process for the preparation of trishydroxyalkyl heterocycles according to Claim 1 and 2, characterized in that that triazolidinedione-3,5 or, the corresponding thioanalogues with ethene oxides of the general formula II R ¹ R ^{3 C} CU) wherein 12 3 4 R, R, R and R have the meaning given in claim 1 to have, optionally reacted in the presence of a catalyst and / or solvent. Le A 19 10i 030037/0281